US20070190306A1 - Organically modified siloxanes and their use for producing preparations for water-repellent impregnations for mineral building materials - Google Patents
Organically modified siloxanes and their use for producing preparations for water-repellent impregnations for mineral building materials Download PDFInfo
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- US20070190306A1 US20070190306A1 US11/673,682 US67368207A US2007190306A1 US 20070190306 A1 US20070190306 A1 US 20070190306A1 US 67368207 A US67368207 A US 67368207A US 2007190306 A1 US2007190306 A1 US 2007190306A1
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- Prior art keywords
- radical
- radicals
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- carbon atoms
- ethyl
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- -1 siloxanes Chemical class 0.000 title claims abstract description 33
- 239000004566 building material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000005470 impregnation Methods 0.000 title claims abstract description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 13
- 239000011707 mineral Substances 0.000 title claims abstract description 13
- 239000005871 repellent Substances 0.000 title claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 150000003254 radicals Chemical class 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 239000003995 emulsifying agent Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000005840 aryl radicals Chemical class 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 4
- 239000003755 preservative agent Substances 0.000 claims description 3
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 2
- 230000002335 preservative effect Effects 0.000 claims 1
- 239000000839 emulsion Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 17
- 230000035515 penetration Effects 0.000 description 17
- 239000011449 brick Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 9
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 0 [1*][Si]([1*])([4*])O[Si]([1*])([1*])OC.[1*][Si]([1*])([4*])O[Si]([1*])([H])O[Si]([1*])([2*][Si]([5*])([5*])[5*])O[Si]([1*])([3*])C Chemical compound [1*][Si]([1*])([4*])O[Si]([1*])([1*])OC.[1*][Si]([1*])([4*])O[Si]([1*])([H])O[Si]([1*])([2*][Si]([5*])([5*])[5*])O[Si]([1*])([3*])C 0.000 description 7
- 238000007792 addition Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 150000004756 silanes Chemical class 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- TXNSZCSYBXHETP-UHFFFAOYSA-N 2-chloro-n-(hydroxymethyl)acetamide Chemical compound OCNC(=O)CCl TXNSZCSYBXHETP-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- HTKSKBNGLPNIAR-UHFFFAOYSA-N C.[H][Si](C)(O[Si](C)(C)C)O[Si](C)(CCCCCCCCCCCCCCC)O[Si](C)(CC[Si](OCC)(OCC)OCC)O[Si](C)(C)O[Si](C)(C)C Chemical compound C.[H][Si](C)(O[Si](C)(C)C)O[Si](C)(CCCCCCCCCCCCCCC)O[Si](C)(CC[Si](OCC)(OCC)OCC)O[Si](C)(C)O[Si](C)(C)C HTKSKBNGLPNIAR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- JXNWYBSGJSDYRQ-UHFFFAOYSA-N [H][Si](C)(O[Si](C)(C)C)O[Si](C)(CCC1=CC=CC=C1)O[Si](C)(CC[Si](OC)(OC)OC)O[Si](C)(C)O[Si](C)(C)C Chemical compound [H][Si](C)(O[Si](C)(C)C)O[Si](C)(CCC1=CC=CC=C1)O[Si](C)(CC[Si](OC)(OC)OC)O[Si](C)(C)O[Si](C)(C)C JXNWYBSGJSDYRQ-UHFFFAOYSA-N 0.000 description 1
- VZXOIFFMKQNFEQ-UHFFFAOYSA-N [H][Si](C)(O[Si](C)(C)C)O[Si](C)(CCCCOC)O[Si](C)(CC[Si](OCC)(OCC)OCC)O[Si](C)(C)O[Si](C)(C)C Chemical compound [H][Si](C)(O[Si](C)(C)C)O[Si](C)(CCCCOC)O[Si](C)(CC[Si](OCC)(OCC)OCC)O[Si](C)(C)O[Si](C)(C)C VZXOIFFMKQNFEQ-UHFFFAOYSA-N 0.000 description 1
- LPIGNNPIZVPDKJ-UHFFFAOYSA-N [H][Si](C)(O[Si](C)(C)C)O[Si](C)(CC[Si](OCC)(OCC)OCC)O[Si](C)(C)O[Si](C)(C)C Chemical compound [H][Si](C)(O[Si](C)(C)C)O[Si](C)(CC[Si](OCC)(OCC)OCC)O[Si](C)(C)O[Si](C)(C)C LPIGNNPIZVPDKJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- ORTFAQDWJHRMNX-UHFFFAOYSA-M oxidooxomethyl Chemical compound [O-][C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-M 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
- C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249955—Void-containing component partially impregnated with adjacent component
- Y10T428/249956—Void-containing component is inorganic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249967—Inorganic matrix in void-containing component
Definitions
- the invention relates to organically modified siloxanes and their use for producing preparations for water-repellent impregnations for mineral building materials, which are based on organomodified siloxane compounds which simultaneously have hydrogen bound to Si atoms and alkoxy groups in the molecule.
- Organosilanes or organosiloxanes have for many years been used for impregnating porous mineral building materials in order to protect the latter from penetration by water. In this hydrophobicizing treatment, it is particularly important that the active substances penetrate deep into the building material and combine chemically or physically with the building material.
- the penetration into the building material is favored when very low molecular weight compounds are used as organosilicon active substances.
- the penetration depth can additionally be improved by the concomitant use of organic solvents which evaporate after treatment of the building material.
- organoalkoxysilanes and/or organoalkoxysiloxanes which can condense under the action of moisture and react with the building material are used as organosilicon compounds.
- the alcohol corresponding to the alkoxy group is eliminated and evaporates into the atmosphere.
- R 1 is an alkyl or aryl radical
- R 2 is an alkyl radical having from 1 to 4 carbon atoms
- a 0.8 to 1.5 and b is ⁇ 2.
- This preparation comprises
- the essential feature of this preparation is that the impregnation is not carried out using an organoalkoxysiloxane whose molecular weight distribution has essentially only a single maximum but instead a mixture of organoalkoxysiloxanes which have different degrees of condensation.
- This preparation can be improved essentially only in respect of the penetration depth which can be achieved in practice.
- This penetration depth is influenced by essentially three factors, namely the solvents used, the porosity of the building materials and the care with which these preparations are employed in practice. It is therefore necessary to measure, in particular, the penetration behavior of improved preparations for impregnation.
- the penetration of the aqueous preparations into the mineral building material is high and comparable to the penetration achieved when using solvent-containing preparations.
- EP-A-0 234 024 (U.S. Pat. No. 4,648,904 and US-Rei-33,759) describes an aqueous silane emulsion for hydrophobicizing ceramic materials which consists essentially of
- silane As particularly preferred silane, mention is made of octyltriethoxysilane. Emulsions of such silanes in which the radical R has more than 6 carbon atoms actually have an increased stability since the hydrolysis rate of these reactive silanes is reduced.
- a disadvantage is that the hydrolysis of these silanes in the building material necessarily also proceeds correspondingly slowly and has to be catalyzed in an appropriate way.
- some building materials e.g. fresh concrete
- this is possible by means of their high alkalinity.
- neutral or weakly alkaline building materials such as fired clinker and numerous types of natural stone.
- anchoring of the silanes to the surface of the building material does not occur without such catalysis.
- the silanes can evaporate from the surface or be removed mechanically. This leads to a depletion of the surface in silanes and thus to a reduction in the hydrophobicization. As a consequence, the water beading effect is weak or not present at all. The water absorption capability of the depleted surface layer is high, so that precisely this layer which is particularly exposed to weathering and mechanical damage is insufficiently protected. These preparations can thus be used only for particular building materials.
- R 3 an alkyl radical having from 1 to 6 carbon atoms
- This impregnation emulsion generally has good beading effects both on alkaline and neutral mineral substrates.
- the impregnation emulsion is stable for only a limited time at a low emulsifier content. If hydrophobicized silica is present in the emulsion, this frequently sediments during storage and makes careful stirring at the place of use, i.e. the building site, necessary.
- the curing catalyst limits the processing latitute of the emulsion in terms of time and can lead to premature curing of the active substance in the emulsion during storage.
- VOC-rich formulations Due to increased environmental awareness, the use of such VOC-rich formulations is increasingly considered to be undesirable. Efforts have therefore been made, in particular, to develop comparable but low-VOC preparations, with this also encompassing volatile solvents.
- the invention therefore provides, firstly, organomodified siloxane compounds of the general formula (I)
- the invention further provides concentrates of aqueous emulsions for the water-repellent impregnation of inorganic and organic substrates, which comprise
- mineral or wood-containing materials and finished parts and also products made therefrom for example stones, slabs, tiles, mortar compositions, concrete compositions, insulation materials for thermal and acoustic insulation.
- the invention does not intend to encompass within the scope of the invention any previously disclosed product, process of making the product or method of using the product, which meets the written description and enablement requirements of the USPTO (35 U.S.C. 112, first paragraph) or the EPO (Article 83 of the EPC), such that applicant(s) reserve the right and hereby disclose a disclaimer of any previously described product, method of making the product or process of using the product.
- Emulsifiers which are concomitantly used according to the invention comprise one or more compounds from the group consisting of nonionogenic emulsifiers, i.e. addition products of alkylene oxides, preferably ethylene oxide, onto compounds having an active hydrogen, e.g. fatty alcohols, alkylphenols such as octylphenol, nonylphenol or dodecylphenol.
- the content of oxyethylene units should be sufficiently high for the HLB of the emulsifiers to be from 6 to 20, in particular from 10 to 18.
- the aqueous emulsion according to the invention can be produced by separately emulsifying the constituents a), b) and d) or emulsifying a mixture of the constituents.
- the emulsifier is advantageously added to the component to be emulsified (or to a mixture thereof) and the emulsifier-containing mixture is heated if appropriate.
- the water c) is then added to this mixture while stirring well.
- the emulsion which is being formed or has been formed can be homogenized by means of suitable stirring apparatuses which preferably operate according to the rotor/stator principle. Colloid mills can also be used for reducing the particle size of the emulsified phase.
- N total chain length of Si chain
- Examples 1 to 4 are stirred separately into the solution, designated as 5a to 5d, and processed by means of an emulsifying machine (slit homogenizer) to give a stable emulsion.
- an emulsifying machine slit homogenizer
- concentrates can be used directly or be adjusted to the desired use concentrations by simple dilution with water. These concentrations are dependent on the type of building materials to be hydrophobicized, in particular their porosity or their absorbency.
- formulations which contain about 10% by weight of compounds of the general formula (I).
- the use testing of building protection compositions comprises assessment of the beading effect, determination of the water absorption using a method based on DIN 52103 (ASTM C97-47) and determination of the penetration depth on five impregnated lime-sand bricks.
- the bricks are cut to the following format: 20 mm ⁇ 70 mm ⁇ 55 mm
- the cut lime-sand bricks are irrigated at room temperature for 24 hours and cleaned with water and a brush until all dust is removed.
- the cleaned test specimens are subsequently dried in a drying oven at 105° C. for 24 hours and then stored at room temperature (about 23° C.) until their weight is constant.
- the cleaned and conditioned lime-sand bricks are immersed for one minute in the ready-to-use solution (containing 10% by weight of the compounds of the general formula (I)).
- the supernatant liquid column here should be from about 10 to 15 mm.
- the impregnated bricks are taken from the bath using the crucible tongs and allowed to dry in air at room temperature on a mesh for 7 days.
- 0.5 ml of distilled water is placed on the surface of the brick by means of a pipette after one day and 7 days after impregnation.
- the outlet of the pipette should gently touch the surface so that the drop does not run off sideways.
- the water drop is shaken off and the beading effect is subsequently assessed.
- the quality of the beading effect is established according to the assessment criteria below (see point 8). The beading effect is determined on all test specimens and the mean is calculated.
- test specimens After storage on a mesh at room temperature for from 7 to 14 days (depending on the substrate), the test specimens are weighed (M1) and placed in a water bath. The bath provided for this has a plastic mesh. The water column above the brick has to be 50 mm. After 24 hours, the bricks are taken from the water bath, the surface water is removed with cleaning paper and the test specimen is weighed (M2).
- test specimens After determination of the water absorption, the test specimens are dried overnight at 105° C. and subsequently split by means of a hammer. The fracture surfaces are wetted with water. The unimpregnated places appear dark, while the impregnated hydrophobic zones are not wetted and remain light in color. If a penetration depth which differs greatly is observed on a test specimen, the arithmetic mean is to be formed.
- the beading effect after 7 days should correspond to the grade 3.
- the result is reported in % by weight.
- the reduction in the water absorption after 24 hours should be at least 70% based on the blank.
- the penetration depth is measured by breaking the brick and subsequently wetting it.
- the unwetted border is measured in mm.
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Abstract
Description
- This application claims benefit under 35 U.S.C. 119(a) of German patent application DE 10 2006 007 018.6, filed on 15 Feb. 2006.
- Any foregoing applications including German patent application DE 10 2006 007 018.6, and all documents cited therein or during their prosecution (“application cited documents”) and all documents cited or referenced in the application cited documents, and all documents cited or referenced herein (“herein cited documents”), and all documents cited or referenced in herein cited documents, together with any manufacturer's instructions, descriptions, product specifications, and product sheets for any products mentioned herein or in any document incorporated by reference herein, are hereby incorporated herein by reference, and may be employed in the practice of the invention.
- Citation or identification of any document in this application is not an admission that such document is available as prior art to the present invention.
- The invention relates to organically modified siloxanes and their use for producing preparations for water-repellent impregnations for mineral building materials, which are based on organomodified siloxane compounds which simultaneously have hydrogen bound to Si atoms and alkoxy groups in the molecule.
- Organosilanes or organosiloxanes have for many years been used for impregnating porous mineral building materials in order to protect the latter from penetration by water. In this hydrophobicizing treatment, it is particularly important that the active substances penetrate deep into the building material and combine chemically or physically with the building material.
- The penetration into the building material is favored when very low molecular weight compounds are used as organosilicon active substances. The penetration depth can additionally be improved by the concomitant use of organic solvents which evaporate after treatment of the building material.
- A high reactivity is achieved when organoalkoxysilanes and/or organoalkoxysiloxanes which can condense under the action of moisture and react with the building material are used as organosilicon compounds. Here, the alcohol corresponding to the alkoxy group is eliminated and evaporates into the atmosphere.
- U.S. Pat. No. 4,486,476 discloses such a preparation having a content of organoalkoxysilanes of the general formula
- where
- a=0.8 to 1.5 and
b is ≦2. - This preparation comprises
-
- a) from 1 to 20% by weight of a mixture of organoalkoxy-siloxanes of the abovementioned formula, which comprises from 25 to 75% by weight of a siloxane whose value of b is from 0.1 to 0.5 and from 75 to 25% by weight of a siloxane whose value of b is from 0.8 to 2.0, with a+b being ≦3,
- b) from 80 to 99% by weight of a solvent which is immiscible with water and
- c) optionally, condensation catalysts known per se.
- The essential feature of this preparation is that the impregnation is not carried out using an organoalkoxysiloxane whose molecular weight distribution has essentially only a single maximum but instead a mixture of organoalkoxysiloxanes which have different degrees of condensation.
- This ensures a high penetration depth and also a high effectiveness, in particular on alkaline building materials, and a good, visible water beading effect.
- This preparation can be improved essentially only in respect of the penetration depth which can be achieved in practice. This penetration depth is influenced by essentially three factors, namely the solvents used, the porosity of the building materials and the care with which these preparations are employed in practice. It is therefore necessary to measure, in particular, the penetration behavior of improved preparations for impregnation.
- Due to increased environmental awareness, the use of organic solvents is increasingly considered to be undesirable. Efforts have therefore been made, in particular, to develop comparable preparations having an aqueous basis.
- Further development work has led to a process which is subject matter of U.S. Pat. No. 4,781,950. This patent document relates to a process for impregnating mineral building materials, in particular masonry, with aqueous solutions of silanols and/or siloxanols which are produced where they are to be used by hydrolysis of alkoxysilanes and/or alkoxysiloxanes. Here, the alkoxysilanes and/or alkoxysiloxanes selected are compounds of the general formula
- where
-
- R1=alkyl radical having from 1 to 8 carbon atoms, with at least 90% of the radicals R1 present in the average molecule being alkyl radicals having from 1 to 4 carbon atoms,
- R2=methyl or ethyl radical,
- a=0 to 1.5,
- b=1.0 to 4.0,
- a+b=2.0 to 4.0,
these are hydrolyzed continuously in an amount corresponding to consumption and the solution obtained is applied within from 3 to 30 minutes after mixing of the reactants to the mineral building material.
- In this type of process, the penetration of the aqueous preparations into the mineral building material is high and comparable to the penetration achieved when using solvent-containing preparations.
- However, these aqueous solutions have to be, as advised in DE-C-36 27 060 (U.S. Pat. No. 4,781,950), prepared at the site of use because of their storage instability.
- The published European patent application EP-A-0 234 024 (U.S. Pat. No. 4,648,904 and US-Rei-33,759) describes an aqueous silane emulsion for hydrophobicizing ceramic materials which consists essentially of
-
- a) from 1 to 40% by weight of a hydrolyzable silane having a molecular weight up to about 500 and the general formula RnSi(R′)4-n, where R is a halogenated or unhalogenated hydrocarbon radical having from 1 to 20 carbon atoms, R′ is an alkoxy radical having from 1 to 3 carbon atoms, a halogen, amino or carboxyl radical, n=1 or 2, or oligomers of these silanes and
- b) from 0.5 to 50% by weight, based on silane, of an emulsifier having an HLB of from 4 to 15 and
- c) water.
- As particularly preferred silane, mention is made of octyltriethoxysilane. Emulsions of such silanes in which the radical R has more than 6 carbon atoms actually have an increased stability since the hydrolysis rate of these reactive silanes is reduced.
- However, a disadvantage is that the hydrolysis of these silanes in the building material necessarily also proceeds correspondingly slowly and has to be catalyzed in an appropriate way. In some building materials, e.g. fresh concrete, this is possible by means of their high alkalinity. However, it is not possible in neutral or weakly alkaline building materials such as fired clinker and numerous types of natural stone. However, anchoring of the silanes to the surface of the building material does not occur without such catalysis.
- The silanes can evaporate from the surface or be removed mechanically. This leads to a depletion of the surface in silanes and thus to a reduction in the hydrophobicization. As a consequence, the water beading effect is weak or not present at all. The water absorption capability of the depleted surface layer is high, so that precisely this layer which is particularly exposed to weathering and mechanical damage is insufficiently protected. These preparations can thus be used only for particular building materials.
- An impregnation emulsion which works well on alkaline and neutral building materials is described in U.S. Pat. No. 5,091,002. It contains from 2.5 to 25% by weight of an alkoxysilane of the general formula
-
R1—Si (OR2)3 - where
-
- R1=an alkyl radical having from 3 to 12 carbon atoms and
- R2=a methyl or ethyl radical,
from 2 to 20% by weight of an alkoxysiloxane of the general formula
- where
- a=0.8 to 1.2 and
b=0.2 to 1.2,
from 0.01 to 5% by weight of an emulsifier,
from 0.01 to 0.1% by weight of fillers having an effective surface area of at least 40 m2/g and from 49.9 to 95.48% by weight of water. - This impregnation emulsion generally has good beading effects both on alkaline and neutral mineral substrates.
- If the effects which can be achieved by means of this emulsion are graded according to the evaluation scheme indicated below, it is found that the best results are achieved when
-
- a) the emulsifier content is low,
- b) hydrophobicized silica and
- c) a curing catalyst for the organosilicon compounds are present in the emulsion.
- However, the impregnation emulsion is stable for only a limited time at a low emulsifier content. If hydrophobicized silica is present in the emulsion, this frequently sediments during storage and makes careful stirring at the place of use, i.e. the building site, necessary.
- This care is not always present. Finally, the curing catalyst limits the processing latitute of the emulsion in terms of time and can lead to premature curing of the active substance in the emulsion during storage.
- Further development work has led to a process which is subject matter of DE-A-40 29 640 (U.S. Pat. No. 5,196,054). This is concerned with the problem of improving the use properties of such impregnation emulsions, in particular the problem of producing storage-stable emulsions which lead to a high beading effect within a short time, generally within one day, without addition of hydrophobicized silica or specific curing catalysts being necessary. These preparations are emulsions containing mixtures of, inter alia, various siloxane compounds which cure by means of a condensation reaction and in the process eliminate volatile alcohols (VOC) in amounts of from 250 to 500 g/l.
- This leads to a low degree of utilization of the active substance and to increased pollution of the environment. In addition, in the case of aqueous systems/emulsions, the storage stability of the systems is limited as a result of the elimination of alcohol, since the emulsions are broken by the free alcohol. This has the consequence that the active substances condense and thus no longer penetrate sufficiently in later use.
- Due to increased environmental awareness, the use of such VOC-rich formulations is increasingly considered to be undesirable. Efforts have therefore been made, in particular, to develop comparable but low-VOC preparations, with this also encompassing volatile solvents.
- It is an object of the invention to discover an environmentally friendly system which hydrophobicizes the substrate and firstly penetrates readily into a mineral or organic building material, has a good beading effect and at the same time offers reduced liberation of volatile organic constituents and cures independently of the nature of the substrate.
- This object is surprisingly achieved by the use of organomodified siloxane compounds which simultaneously contain hydrogen and alkoxy groups in the molecule.
- The invention therefore provides, firstly, organomodified siloxane compounds of the general formula (I)
- where
-
- the radicals R1 are identical or different radicals selected from the group consisting of linear or branched, saturated or monounsaturated or polyunsaturated alkyl, aryl, alkylaryl or arylalkyl radicals having carbon atoms selected from the group consisting of from 1 to 20 carbon atoms, and from 1 to 10 carbon atoms, and haloalkyl groups having carbon atoms selected from 1 to 20 carbon atoms, 1 to 10 carbon atoms and 1-4 carbon atoms. One embodiment of R1 is ≧90% methyl groups,
- the radicals R2 are identical or different alkylene radicals which have carbon atoms selected from the group consisting of from 1 to 20 carbon atoms, from 1 to <10 carbon atoms, from 1 to 5 carbon atoms, and the ether, ester, urethane or amide groups, and ethylene radicals,
- R3 is an oxyalkylene radical of the formula (II),
-
-
- where
- the radicals R3a can each be, independently of one another, hydrogen or a branched or unbranched, unsubstituted or heteroatom-substituent-bearing, saturated or unsaturated alkyl or aryl radical which have carbon atoms selected from the group consisting of from 1 to 10 carbon atoms, 2 carbon atom (ethyl) and 1 carbon atom (ethyl) and
- R6a, R6b can each be, independently of one another, hydrogen, a branched or unbranched, unsubstituted or heteroatom-substituent-bearing, saturated or unsaturated alkyl or aryl radical which have 1-10 carbon atoms, (in another embodiment of the invention R6a, R6b can each be, independently of one another, hydrogen, methyl and/or ethyl radicals) and
- k is from 2 to 11,
- a, b are each, independently of one another, a number in the range from 1 to 4 and
- na, nb are each, independently of one another, a number in the range selected from the group consisting of from 0 to 50, where 1<na+nb≦50, 1<na+nb≦30, and 1<na+nb≦15,
- with a random or blockwise arrangement of the oxyalkylene units being able to be present,
the radicals R4 are each, independently of one another, R1, —R2—Si(R5)3, R3 or H.
- the radicals R5 are identical or different alkyl, alkoxy, aryl, aryloxy or alkenyl radicals having from 1 to 20 carbon atoms, with the proviso that at least one R5 is an alkoxy group (in another embodiment of the invention R5 is methoxy and/or ethoxy),
- n is a number selected from the range consisting of from 1 to 20, from 1 to 10, and from 1 to 5,
- m is from 0 to 20, with m only being 0 when R4 is the radical —R2—Si(R5)3 and otherwise is selected from the group consisting of being ≧1, from 0 to 10, and from <5,
- o is a number selected from the range consisting of from 0 to 20, from 1 to 10, and ≦5,
- p is a number selected from the range consisting of from 1 to 200, from 10 to 100, and from 10 to 50.
-
- The invention further provides concentrates of aqueous emulsions for the water-repellent impregnation of inorganic and organic substrates, which comprise
-
- a) from 10 to 80% by weight, (in another embodiment of the invention, from 20 to 60% by weight, or from 30 to 50% by weight), of a compound of the general formula (I), (in another embodiment of the invention, the compound of general formula (I) are compounds in which R4 corresponds to R2—Si(R5)3, R5 is an alkoxy function and n<5, m=0 and o+p<50 or R5 is an alkoxy function and n<5, m=1 to 5 and o+p<50),
- b) from 0.5 to 10% by weight of an emulsifier or emulsifier mixture, (in another embodiment of the invention, from 1.0 to 5.0% by weight, or from 2.0 to 3.5% by weight),
- c) from 10 to 89.5% by weight of water and, optionally,
- d) from 0 to 0.5% by weight of preservatives.
- It is possible to impregnate, i.e. hydrophobicize, all inorganic and organic substrates by means of the compounds of the invention, in particular the aqueous concentrates and/or the formulations which have been diluted to use concentration.
- According to the invention, preference is given to mineral or wood-containing materials and finished parts and also products made therefrom, for example stones, slabs, tiles, mortar compositions, concrete compositions, insulation materials for thermal and acoustic insulation.
- It is further noted that the invention does not intend to encompass within the scope of the invention any previously disclosed product, process of making the product or method of using the product, which meets the written description and enablement requirements of the USPTO (35 U.S.C. 112, first paragraph) or the EPO (Article 83 of the EPC), such that applicant(s) reserve the right and hereby disclose a disclaimer of any previously described product, method of making the product or process of using the product.
- It is noted that in this disclosure and particularly in the claims and/or paragraphs, terms such as “comprises”, “comprised”, “comprising” and the like can have the meaning attributed to it in U.S. Patent law; e.g., they can mean “includes”, “included”, “including”, and the like; and that terms such as “consisting essentially of” and “consists essentially of” have the meaning ascribed to them in U.S. Patent law, e.g., they allow for elements not explicitly recited, but exclude elements that are found in the prior art or that affect a basic or novel characteristic of the invention.
- Emulsifiers which are concomitantly used according to the invention comprise one or more compounds from the group consisting of nonionogenic emulsifiers, i.e. addition products of alkylene oxides, preferably ethylene oxide, onto compounds having an active hydrogen, e.g. fatty alcohols, alkylphenols such as octylphenol, nonylphenol or dodecylphenol. The content of oxyethylene units should be sufficiently high for the HLB of the emulsifiers to be from 6 to 20, in particular from 10 to 18.
- It is possible to use all preservatives known in the prior art. According to the invention, preference is given to products of the group: combination of heterocycles and methylol derivatives (for example N-methylolchloroacetamide, 5-chloro-2-methyl-2-isothiazol-3-one) and mixtures of hemiacetals with nonhazardous additions (for example [1,2-ethanediylbis-(oxy)]bismethanol).
- The aqueous emulsion according to the invention can be produced by separately emulsifying the constituents a), b) and d) or emulsifying a mixture of the constituents. Here, the emulsifier is advantageously added to the component to be emulsified (or to a mixture thereof) and the emulsifier-containing mixture is heated if appropriate. The water c) is then added to this mixture while stirring well. The emulsion which is being formed or has been formed can be homogenized by means of suitable stirring apparatuses which preferably operate according to the rotor/stator principle. Colloid mills can also be used for reducing the particle size of the emulsified phase.
- The invention is further described by the following non-limiting examples which further illustrate the invention, and are not intended, nor should they be interpreted to, limit the scope of the invention.
- The following examples serve to illustrate the invention but do not constitute any restriction.
- In the following:
- Reaction of an internal S1H-siloxane (N=27.5, M-D20.5-D′5-M; SiH value: 0.248%) with styrene (Brenntag) and Dynasilan® VTMO (vinyltrimethoxysilane, Degussa AG) using a Pt-containing catalyst.
- 1016 g of the SiH siloxane (SiH value: 0.248%), 52 g of styrene and Karstedt catalyst (10 ppm of Pt based on the batch) are placed in a reaction vessel and heated to 80° C. The exothermic reaction which occurs leads to a temperature increase to about 103° C. After 3 hours, 126 g of Dynasilan® VTMO are added dropwise over a period of 3 hours, with the temperature not being allowed to exceed 110° C. After the addition is complete, the mixture is allowed to undergo an after-reaction at 110° C. for 1 hour. Distilling off the volatile compounds and filtering the product gives a clear, slightly yellowish liquid which has an SiH value of 0.097%.
- Reaction of an internal SiH-siloxane (N=27.5, M-D20.5-D′5-M; SiH value: 0.248%) with an allyl alcohol-initiated, methyl end-capped, propylene oxide-containing polyether (—CH2═CH—CH2—(OC3H6)18—OMe; Mw about 1100) and Dynasilan® VTEO (vinyltriethoxysilane, Degussa AG) using a Pt-containing catalyst.
- 691 g of the S1H-siloxane (SiH value: 0.248%), 348 g of allyl alcohol-initiated, methyl end-capped, propylene oxide-containing polyether (CH2═CH—CH2—(OC3H6)18—OMe; Mw about 1100) and Karstedt catalyst (10 ppm of Pt based on the batch) are placed in a reaction vessel and heated to 80° C. The exothermic reaction which occurs leads to a temperature increase to about 100° C. After 3 hours, 110 g of Dynasilan® VTEO are added dropwise over a period of 3 hours, with the temperature not being allowed to exceed 110° C. After the addition is complete, the mixture is allowed to undergo an after-reaction at 110° C. for 1 hour. Distilling off the volatile compounds and filtering the product gives a clear, slightly yellowish liquid which has an SiH value of 0.08%.
- Reaction of an internal S1H-siloxane (N=27.5, M-D20.5-D′5-M; SiH value: 0.248%) with 1-hexadecene and Dynasilan® VTEO (vinyltriethoxysilane, Degussa AG) using a Pt-containing catalyst.
- 955 g of the SiH-siloxane (SiH value: 0.248%), 106 g of 1-hexadecene and Karstedt catalyst (10 ppm of Pt based on the batch) are placed in a reaction vessel and heated to 80° C. The exothermic reaction which occurs leads to a temperature increase to about 95° C. After 3 hours, 152 g of Dynasilan® VTEO are added dropwise over a period of 3 hours, with the temperature not being allowed to exceed 110° C. After the addition is complete, the mixture is allowed to undergo an after-reaction at 110° C. for 2 hours.
- Distilling off the volatile compounds and filtering the product gives a clear, colorless liquid which has an SiH value of 0.095%.
- Reaction of an internal S1H-siloxane (N=27.5, M-D20.5-D′5-M; SiH value: 0.248%) with Dynasilan® VTEO (vinyltri-ethoxyilane, Degussa AG) using a Pt-containing catalyst. 305 g of the S1H-siloxane (SiH value: 0.248%) and Karstedt catalyst (10 ppm of Pt based on the batch) are placed in a reaction vessel and heated to 100° C. 45.6 g of VTEO are subsequently added dropwise over a period of 1 hour, with the temperature not being allowed to exceed 110° C. After the addition is complete, the mixture is allowed to undergo an after-reaction at 110° C. for 2 hours.
- Distilling off the volatile compounds and filtering the product gives a clear, colorless liquid which has an SiH value of 0.15%.
- Production of the emulsions for the use test. 19 g of an emulsifier mixture comprising an ethoxylated triglyceride having an HLB of 18 and an ethoxylated fatty alcohol having an HLB of 11 in a weight ratio of 6:4 are dissolved in 479 g of water.
- Examples 1 to 4 are stirred separately into the solution, designated as 5a to 5d, and processed by means of an emulsifying machine (slit homogenizer) to give a stable emulsion.
- These concentrates can be used directly or be adjusted to the desired use concentrations by simple dilution with water. These concentrations are dependent on the type of building materials to be hydrophobicized, in particular their porosity or their absorbency.
- In general, these are formulations which contain about 10% by weight of compounds of the general formula (I).
- The use testing of building protection compositions comprises assessment of the beading effect, determination of the water absorption using a method based on DIN 52103 (ASTM C97-47) and determination of the penetration depth on five impregnated lime-sand bricks.
- The formulations were tested according to the following test procedure:
- The bricks are cut to the following format:
20 mm×70 mm×55 mm - Tap water: 400 g
- (130 mm×90 mm×90 mm; W×H×D)
- The cut lime-sand bricks are irrigated at room temperature for 24 hours and cleaned with water and a brush until all dust is removed. The cleaned test specimens are subsequently dried in a drying oven at 105° C. for 24 hours and then stored at room temperature (about 23° C.) until their weight is constant.
- The cleaned and conditioned lime-sand bricks are immersed for one minute in the ready-to-use solution (containing 10% by weight of the compounds of the general formula (I)). The supernatant liquid column here should be from about 10 to 15 mm. The impregnated bricks are taken from the bath using the crucible tongs and allowed to dry in air at room temperature on a mesh for 7 days.
- To determine the beading effect, 0.5 ml of distilled water is placed on the surface of the brick by means of a pipette after one day and 7 days after impregnation. The outlet of the pipette should gently touch the surface so that the drop does not run off sideways. After 10 minutes, the water drop is shaken off and the beading effect is subsequently assessed. The quality of the beading effect is established according to the assessment criteria below (see point 8). The beading effect is determined on all test specimens and the mean is calculated.
- After storage on a mesh at room temperature for from 7 to 14 days (depending on the substrate), the test specimens are weighed (M1) and placed in a water bath. The bath provided for this has a plastic mesh. The water column above the brick has to be 50 mm. After 24 hours, the bricks are taken from the water bath, the surface water is removed with cleaning paper and the test specimen is weighed (M2).
- The result is reported in % by weight. A blank is always also determined.
- After determination of the water absorption, the test specimens are dried overnight at 105° C. and subsequently split by means of a hammer. The fracture surfaces are wetted with water. The unimpregnated places appear dark, while the impregnated hydrophobic zones are not wetted and remain light in color. If a penetration depth which differs greatly is observed on a test specimen, the arithmetic mean is to be formed.
-
- 0=The water drop cannot be placed on the surface of the brick.
- 1=The water drop is not absorbed; no wetting of the surface by the drop.
- 2=The water drop is not absorbed; about half of the surface of the brick under the water drop is wetted.
- 3=The water drop is not absorbed; the surface of the brick under the water drop is fully wetted.
- 4=Less than 10% of the water drop is absorbed; dark coloration of the surface of the brick under the water drop.
- 5=50% of the water drop is absorbed.
- 6=The water drop is completely absorbed.
- The beading effect after 7 days should correspond to the grade 3.
- Calculation formula for the water absorption (WA)
-
- The result is reported in % by weight. The reduction in the water absorption after 24 hours should be at least 70% based on the blank.
- The penetration depth is measured by breaking the brick and subsequently wetting it. The unwetted border is measured in mm.
-
-
Water absorption after storage Beading effect Penetration under pressurized [0 = good to depth water Product 6 = poor] [mm] [%] Example 5c 3 1.8 1.0 (reduction by 80%) Example 5d 3 2 0.9 (reduction by 82%) Blank 6 — 5.0 -
-
Water absorption after storage Beading effect Penetration under pressurized [0 = good to depth water Product 6 = poor] [mm] [%] Example 5c 2 2.5 1.0 (reduction by 93%) Example 5d 2 2.3 1.0 (reduction by 93%) Blank 6 — 14.5 -
-
Water absorption after storage Beading effect Penetration under pressurized [0 = good to depth water Product 6 = poor] [mm] [%] Example 5a 1 >10 0.9 (reduction by 93%) Example 5d 2 >10 0.7 (reduction by 95%) Blank 6 — 13.5
Having thus described in detail various embodiments of the present invention, it is to be understood that the invention defined by the above paragraphs is not to be limited to particular details set forth in the above description as many apparent variations thereof are possible without departing from the spirit or scope of the present invention.
Claims (17)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102006007018.6 | 2006-02-15 | ||
DE200610007018 DE102006007018A1 (en) | 2006-02-15 | 2006-02-15 | Organically modified siloxanes and their use for the preparation of preparations for water-repellent impregnations for mineral building materials |
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US20070190306A1 true US20070190306A1 (en) | 2007-08-16 |
US7361777B2 US7361777B2 (en) | 2008-04-22 |
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DE (2) | DE102006007018A1 (en) |
ES (1) | ES2313688T3 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101643639A (en) * | 2008-08-05 | 2010-02-10 | 赢创戈尔德施米特有限公司 | Water repellent treatment for building elements containing mineral fibers |
WO2015150409A1 (en) | 2014-03-31 | 2015-10-08 | Evonik Degussa Gmbh | Adhesion promoter for metal-plastic hybrid components |
US11352510B2 (en) | 2017-10-06 | 2022-06-07 | Evonik Operations Gmbh | Aqueous dispersion containing silicon dioxide and trimethyl-1,6-hexamethylendiamine |
US20230042027A1 (en) * | 2019-12-11 | 2023-02-09 | Adaptive Surface Technologies, Inc. | Side chain functionalized organosiloxane polymers, coating compositions and ice-phobic coatings thereof |
Families Citing this family (15)
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DE102008000287A1 (en) * | 2008-02-13 | 2009-08-20 | Evonik Goldschmidt Gmbh | Reactive, liquid ceramic binder |
DE102008001786A1 (en) * | 2008-05-15 | 2009-11-26 | Evonik Goldschmidt Gmbh | Use of organomodified siloxane block copolymers as a care active substance for the care of human or animal body parts |
DE102008041020A1 (en) * | 2008-08-06 | 2010-02-11 | Evonik Goldschmidt Gmbh | Use of polysiloxanes with quaternary ammonium groups to protect animal or human hair from heat damage |
DE102008042381A1 (en) * | 2008-09-26 | 2010-04-01 | Evonik Goldschmidt Gmbh | Emulsifier systems for cosmetic and pharmaceutical oil-in-water emulsions |
DE102008063965C5 (en) * | 2008-12-19 | 2019-02-21 | Evonik Degussa Gmbh | Hydrophobic cementitious compositions |
DE102010062156A1 (en) | 2010-10-25 | 2012-04-26 | Evonik Goldschmidt Gmbh | Polysiloxanes with nitrogen-containing groups |
RU2456309C1 (en) * | 2011-04-04 | 2012-07-20 | Государственное образовательное учреждение высшего профессионального образования "Московский государственный текстильный университет имени А.Н. Косыгина" | Phenoxyethanol oligoethoxysiloxane derivatives for modifying fibre materials and production method thereof |
DE102011078382A1 (en) | 2011-06-30 | 2013-01-03 | Evonik Goldschmidt Gmbh | Microemulsion of quaternary ammonium group-containing polysiloxanes, their preparation and use |
DE102011110100A1 (en) | 2011-08-12 | 2013-02-14 | Evonik Goldschmidt Gmbh | Process for the preparation of polysiloxanes with nitrogen-containing groups |
DE102013206175A1 (en) | 2013-04-09 | 2014-10-09 | Evonik Industries Ag | Polysiloxane-polyether copolymers having amino and / or quaternary ammonium groups in the polyether part and process for their preparation |
DE102013218134A1 (en) | 2013-09-11 | 2015-03-12 | Evonik Industries Ag | Coating compositions containing polysiloxane quats |
DE102013218981A1 (en) | 2013-09-20 | 2015-03-26 | Evonik Industries Ag | Room temperature curing silicone-polyester binder |
DE102013218976A1 (en) | 2013-09-20 | 2015-04-16 | Evonik Industries Ag | Hydroxyl-containing silicone-polyester-acrylate binder |
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US4486476A (en) * | 1983-04-11 | 1984-12-04 | Th. Goldschmidt Ag | Preparation for making inorganic building materials water-repellent |
US4781950A (en) * | 1986-08-09 | 1988-11-01 | Th. Goldschmidt Ag | Method for impregnating mineral building materials |
US5091002A (en) * | 1989-04-08 | 1992-02-25 | Th. Goldschmidt Ag | Preparation for the water-repellent impregnation of porous mineral building materials |
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US4648904A (en) | 1986-02-14 | 1987-03-10 | Scm Corporation | Aqueous systems containing silanes for rendering masonry surfaces water repellant |
DE4029640A1 (en) | 1990-09-19 | 1992-03-26 | Goldschmidt Ag Th | PREPARATION FOR WATER REPELLENT IMPREGNATION OF POROESER MINERAL BUILDING MATERIALS |
FR2806930B1 (en) * | 2000-04-04 | 2002-06-28 | Rhodia Chimie Sa | USE OF A BORON DERIVATIVE AS A THERMOACTIVABLE CATALYST FOR THE POLYMERIZATION AND/OR CROSS-LINKING OF SILICONE BY DEHYDROGENOCONDENSATION |
US6482912B2 (en) * | 2001-01-29 | 2002-11-19 | Ndsu Research Foundation | Method of preparing aminofunctional alkoxy polysiloxanes |
DE10312636A1 (en) * | 2003-03-21 | 2004-09-30 | Goldschmidt Ag | Process for the implementation of polyorganosiloxanes |
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2006
- 2006-02-15 DE DE200610007018 patent/DE102006007018A1/en not_active Withdrawn
-
2007
- 2007-02-02 AT AT07002249T patent/ATE407184T1/en not_active IP Right Cessation
- 2007-02-02 ES ES07002249T patent/ES2313688T3/en active Active
- 2007-02-02 DE DE200750000091 patent/DE502007000091D1/en active Active
- 2007-02-02 EP EP20070002249 patent/EP1820832B1/en active Active
- 2007-02-12 US US11/673,682 patent/US7361777B2/en active Active
Patent Citations (3)
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US4486476A (en) * | 1983-04-11 | 1984-12-04 | Th. Goldschmidt Ag | Preparation for making inorganic building materials water-repellent |
US4781950A (en) * | 1986-08-09 | 1988-11-01 | Th. Goldschmidt Ag | Method for impregnating mineral building materials |
US5091002A (en) * | 1989-04-08 | 1992-02-25 | Th. Goldschmidt Ag | Preparation for the water-repellent impregnation of porous mineral building materials |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101643639A (en) * | 2008-08-05 | 2010-02-10 | 赢创戈尔德施米特有限公司 | Water repellent treatment for building elements containing mineral fibers |
EP2151420A3 (en) * | 2008-08-05 | 2010-12-29 | Evonik Goldschmidt GmbH | Water repellent treatment for building elements containing mineral fibres |
WO2015150409A1 (en) | 2014-03-31 | 2015-10-08 | Evonik Degussa Gmbh | Adhesion promoter for metal-plastic hybrid components |
US10246575B2 (en) | 2014-03-31 | 2019-04-02 | Evonik Degussa Gmbh | Metal-plastic hybrid component |
US11352510B2 (en) | 2017-10-06 | 2022-06-07 | Evonik Operations Gmbh | Aqueous dispersion containing silicon dioxide and trimethyl-1,6-hexamethylendiamine |
US20230042027A1 (en) * | 2019-12-11 | 2023-02-09 | Adaptive Surface Technologies, Inc. | Side chain functionalized organosiloxane polymers, coating compositions and ice-phobic coatings thereof |
US11891486B2 (en) * | 2019-12-11 | 2024-02-06 | Adaptive Surface Technologies, Inc. | Side chain functionalized organosiloxane polymers, coating compositions and ice-phobic coatings thereof |
Also Published As
Publication number | Publication date |
---|---|
EP1820832B1 (en) | 2008-09-03 |
ES2313688T3 (en) | 2009-03-01 |
EP1820832A1 (en) | 2007-08-22 |
ATE407184T1 (en) | 2008-09-15 |
US7361777B2 (en) | 2008-04-22 |
DE102006007018A1 (en) | 2007-08-16 |
DE502007000091D1 (en) | 2008-10-16 |
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